Arthropodicidal carboxanilides

ABSTRACT

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful as arthropodicides wherein A is H; E is H or C 1 -C 3  alkyl; or A and E can be taken together to form —CH 2 —, —CH 2 CH 2 —, —O—, —S—, —S(O)—, —S(O) 2 —, —NR 8 —, —OCH 2 —, —SCH 2 —, —N(R 8 )CH 2 —, substituted —CH 2 — and substituted —CH 2 CH 2 —, the substituents independently selected from 1-2 halogen and 1-2 methyl; W is N or CR 4 ; X is CR 5 R 6 , O, S, NR 7  or a direct bond, provided that when W is N, then X is other than a direct bond; Y is H, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 3  alkylsulfonyl, C 3 -C 6  cycloalkyl, C 3 -C 6  cycloalkylalkyl, NR 9 R 10 , N═CR 11 R 12 , OR 7 , COR 13 , CO 2 R 14  or C 1 -C 6  alkyl substituted by at least one group selected from halogen, C 1 -C 3  alkoxy, CN, NO 2 , S(O) r R 15 , COR 13 , CO 2 R 14  and optionally substituted phenyl; Z is O or S; and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , G, n and r are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling arthropods which involves contacting the arthropods or their environment with an effective amount of a compound of Formula (I).

BACKGROUND OF THE INVENTION

This invention relate's to certain carboxanilides, their N-oxides,agriculturally suitable salts and compositions, and methods of their useas arthropodicides in both agronomic and nonagronomic environments.

The control of arthropod pests is extremely important in achieving highcrop efficiency. Arthropod damage to growing and stored agronomic cropscan cause significant reduction in productivity and thereby result inincreased costs to the consumer. The control of arthropod pests inforestry, greenhouse crops, ornamentals, nursery crops, stored food andfiber products, livestock, household, and public and animal health isalso important. Many products are commercially available for thesepurposes, but the need continues for new compounds which are moreeffective, less costly, less toxic, environmentally safer or havedifferent modes of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula I including allgeometric and stereoisomers, N-oxides, and agriculturally suitable saltsthereof, agricultural compositions containing them and their use tocontrol arthropods in agronomic and nonagronomic environments

wherein:

A is H;

E is H or C₁-C₃ alkyl; or

A and E can be taken together to form —CH₂—, —CH₂CH₂—, —O—, —S—, —S(O)—,—S(O)₂—, —NR⁸—, —OCH₂—, —SCH₂—, —N(R⁸)CH₂—, substituted —CH₂— andsubstituted —CH₂CH₂—, the substituents on each carbon independentlyselected from 1-2 halogen and 1-2 methyl;

G is selected from the group consisting of

W is N or CR⁴;

X is CR⁵R⁶, O, S, NR⁷ or a direct bond, provided that when W is N, thenX is other than a direct bond;

Y is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₃ alkylsulfonyl,C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, NR⁹R¹⁰, N═CR¹¹R¹², OR⁷, COR¹³,CO₂R¹⁴ or C₁-C₆ alkyl substituted by at least one group selected fromhalogen, C₁-C₃ alkoxy, CN, NO₂, S(O)_(r)R¹⁵, COR¹³, CO₂R¹⁴ andoptionally substituted phenyl;

Z is O or S;

each R¹ and R² is independently selected from the group consisting ofC₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, halogen, CN, NO₂, OR¹⁶, S(O)_(r)R¹⁵,OS(O)₂R¹⁵, CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, SO₂NR⁹R¹⁰, SF₅, optionallysubstituted phenyl and optionally substituted benzyl; or when m or n is2, (R¹)₂ can be taken together or (R²)₂ can be taken together as—OCH₂O—, —OCF₂O—, —OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O—;

R³ is selected from the group consisting of J, C(R¹⁷)═N—O—R¹⁸, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl,C₂-C₆ alkoxylalkyl, C₃-C₈ alkoxycarbonylalkyl, CO₂R¹⁴, C(O)R¹³,C(O)NR⁹R¹⁰, C(S)NR⁹R¹⁰, C(S)R¹³, C(S)SR¹³, CN, and optionallysubstituted phenyl; or R³ is C₂-C₆ epoxyalkyl optionally substitutedwith a group selected from C₁-C₃ alkyl, CN, C(O)R¹³, CO₂R¹⁴ andoptionally substituted phenyl; or R³ is C₁-C₆ alkyl substituted with agroup selected from C(O)NR⁹R¹⁰, COR¹³, CO₂R¹⁴, S(O)_(m)R¹⁵, SCN, CN,C₁-C₂ haloalkoxy, SiR¹⁹R²⁰R²¹, NR⁹R¹⁰, NO₂, OC(O)R¹³, —P(O)(OR²²)₂,optionally substituted phenyl, and J;

J is a nonaromatic or aromatic 5- or 6-membered heterocyclic ring,bonded through carbon or nitrogen, containing 1-4 heteroatomsindependently selected from the group consisting of 0-2 oxygen, 0-2sulfur and 0-4 nitrogen, optionally containing one carbonyl moiety andoptionally substituted;

R⁴, R⁵ and R⁶ are each independently H or C₁-C₄ alkyl;

each R⁷ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₁-C₄ alkoxy, SO₂NR⁹R¹⁰, SO₂R¹³, COR⁹, CONR⁹R¹⁰, CO₂R¹³,optionally substituted phenyl or optionally substituted benzyl;

each R⁸ is independently H, C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl, CO₂R¹³,SO₂R¹³, or optionally substituted benzyl;

each R⁹ and each R¹¹ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl oroptionally substituted phenyl;

each R¹⁰ and each R¹² is independently H or C₁-C₄ alkyl; or

each pair of R⁹ and R¹⁰ when attached to the same atom or each pair ofR¹¹ and R¹² when attached to the same atom independently can be takentogether as —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂— or—CH₂CH₂OCH₂CH₂—, each of which is optionally and independentlysubstituted with 1 or 2 CH₃ groups;

each R¹³ and each R¹⁵ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkylor optionally substituted phenyl;

each R¹⁴ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or optionallysubstituted benzyl;

R¹⁶ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, optionallysubstituted phenyl and optionally substituted benzyl;

R¹⁷ is selected from the group consisting of H, Cl, C₁-C₄ alkyl, C₁-C₄alkoxy, C₁-C₂ thioalkyl and CN;

R¹⁸ is selected from the group consisting of H, C₁-C₄ alkyl, C₂-C₃alkylcarbonyl and C₂-C₃ alkoxycarbonyl;

R¹⁹ and R²⁰ are each independently C₁-C₃ alkyl;

R²¹ is selected from the group consisting of H, C₁-C₃ alkyl andoptionally substituted phenyl;

each R²² is independently H or C₁-C₄ alkyl;

each m and n are independently 1 to 3; and

r is 0, 1 or 2.

DETAILS OF THE INVENTION

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. The term “1-2alkyl” indicates that one or two of the available positions for thatsubstituent may be alkyl which are independently selected. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy”includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy andthe different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl”denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” includeCH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers. “Alkylthioalkyl” denotes alkylthiosubstitution on alkyl. Examples of “alkylthioalkyl” include CH₃SCH₂,CH₃SCH₂CH₂, CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂.“Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group.Examples of “alkylsulfinyl” include CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O),(CH₃)₂CHS(O) and the different butylsulfinyl, pentylsulfinyl andhexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH₃S(O)₂,CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂ and the differentbutylsulfonyl, pentylsulfonyl and hexylsulfinyl isomers. “Cyanoalkyl”denotes an alkyl group substituted with one cyano group. Examples of“cyanoalkyl” include NCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂. “Cycloalkyl”includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, andcyclohexyl. Examples of“cycloalkylalkyl” include cyclopropylmethyl,cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chainor branched alkyl groups. Examples of “cycloalkylalkoxy” includecyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moietiesbonded to straight-chain or branched alkoxy groups. Examples of“alkylcarbonyl” include C(O)CH₃, C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂.Examples of “allcoxycarbonyl” include CH₃OC(═O), CH₃CH₂OC(═O),CH₃CH₂CH₂OC(═O), (CH₃)₂CHOC(═O) and different butoxy- or pentoxycarbonylisomers. Examples of “alkoxycarbonylalkyl” include CH₃OC(═O)CH₂,CH₃CH₂OC(═O)CH₂, CH₃OC(═O)CH₂CH₂, CH₃CHOC(═O)CH₂CH₂ and the differentpropoxy-, butoxy- or pentoxycarbonyl isomers.

The term “halogen”, either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine. The term“1-2 halogen” indicates that one or two of the available positions forthat substituent may be halogen which are independently selected.Further, when used in compound words such as “haloalkyl”, said alkyl maybe partially or fully substituted with halogen atoms which may be thesame or different. Examples of “haloalkyl” include F₃C, ClCH₂, CF₃CH₂and CF₃CCl₂. The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”, andthe like, are defined analogously to the term “haloalkyl”. Examples of“haloalkenyl” include (Cl)₂C═CHCH₂ and CF₃CH₂CH═CHCH₂. Examples of“haloalkynyl” include HC≡CCHCl, CF₃C≡C, CCl₃C≡C and FCH₂C≡CCH₂. Examplesof “haloalkoxy” include CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O.

The term “aromatic ring” denotes fully unsaturated carbocycles andheterocycles in which the ring is aromatic (where aromatic indicatesthat the Hückel rule is satisfied for the ring system). The term“aromatic heterocyclic ring” includes fully aromatic heterocycles (wherearomatic indicates that the Hückel rule is satisfied). The term“nonaromatic heterocyclic ring” denotes fully saturated heterocycles aswell as partially or fully unsaturated heterocycles where the Hückelrule is not satisfied. The heterocyclic ring systems can be attachedthrough any available carbon or nitrogen by replacement of a hydrogen onsaid carbon or nitrogen. The term “benzyl” denotes a —CH₂C₆H₅ moiety inwhich the C₆H₅ ring is aromatic.

One skilled in the art will appreciate that not all nitrogen containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethydioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 6. Forexample, C₁-C₃ alkylsulfonyl designates methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄alkoxyalkyl designates the various isomers of an alkyl group substitutedwith an alkoxy group containing a total of four carbon atoms, examplesincluding CH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. In the above recitations,when a compound of Formula I is comprised of one or more heterocyclicrings, all substituents are attached to these rings through anyavailable carbon or nitrogen by replacement of a hydrogen on said carbonor nitrogen.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents. Further, when the subscript indicates arange, e.g. (R)_(i-j), then the number of substituents may be selectedfrom the integers between i and j inclusive.

When a group contains a substituent which can be hydrogen, for exampleR⁴ or R⁷, then, when this substituent is taken as hydrogen, it isrecognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. Accordingly, the present invention comprises compoundsselected from Formula I, N-oxides and agriculturally suitable saltsthereof. The compounds of the invention may be present as a mixture ofstereoisomers, individual stereoisomers, or as an optically active form.

The salts of the compounds of the invention include acid-addition saltswith inorganic or organic acids such as hydrobromic, hydrochloric,nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic,malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic orvaleric acids. The salts of the compounds of the invention also includethose formed with organic bases (e.g., pyridine, ammonia, ortriethylamine) or inorganic bases (e.g., hydrides, hydroxides, orcarbonates of sodium, potassium, lithium, calcium, magnesium or barium)when the compound contains an acidic group such as a carboxylic acid orphenol.

In Formula I, the term “optionally substituted” in reference to certainphenyl, benzyl or J rings (see the definitions of Y, J, R¹, R², R³, R⁷,R⁸, R⁹, R¹¹, R¹³, R¹⁴, R¹⁵, R¹⁶ and R²¹) refers to a phenyl, benzyl or Jring that is unsubstituted, or is substituted with at least onenon-hydrogen group that does not extinguish the arthropodicidal activitypossessed by the analog in which the phenyl, benzyl or J ring isunsubstituted. In the case of a phenyl ring or a benzyl ring, theoptional non-hydrogen group is attached to a carbon atom containedwithin the aromatic ring. In the case of J, a nonaromatic or aromatic 5-or 6-membered heterocyclic ring, bonded through carbon or nitrogen,containing 1-4 heteroatoms independently selected from the groupconsisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, optionallycontaining one carbonyl moiety and optionally substituted, the optionalnon-hydrogen group is attached to either a carbon atom or a nitrogenwithin the ring. Examples of optionally substituted phenyl, benzyl or Jrings are those wherein said rings are optionally substituted with R²³and optionally substituted with R²⁴, wherein

each R²³ is independently selected from the group consisting of 1-2halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyland C₁-C₂ haloalkylsulfonyl; and

each R²⁴ is independently selected from the group consisting of halogen,C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy.

Examples of phenyl, benzyl or J rings wherein said rings are optionallysubstituted with R²³ and/or R²⁴ include the rings illustrated in Exhibit1 as a phenyl ring optionally substituted with R²³ and/or R²⁴, a benzylring optionally substituted with R²³ and/or R²⁴, 5- or 6-memberedaromatic heterocyclic rings (J-1 to J-28), and 5- or 6-memberednonaromatic heterocyclic rings optionally containing one carbonyl moiety(J-29 to J-50). As with the carbon atoms in the ring, the nitrogen atomsthat require substitution to fill their valence are substituted withhydrogen or with R²³ and/or R²⁴. Although the R²³ and/or R²⁴ groups areshown in the structures illustrated in Exhibit 1, it is noted that R²³and/or R²⁴ do not need to be present since they are optionalsubstituents.

Exhibit 1

Preferred compounds for reasons of better activity and/or ease ofsynthesis are:

Preferred 1. Compounds of Formula I above, and agriculturally suitablesalts thereof, wherein:

Y is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₃ alkylsulfonyl,C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, NR⁹R¹⁰, N≡CR¹¹R¹², OR⁷, COR¹³,CO₂R¹⁴ or C₁-C₆ alkyl substituted by at least one group selected fromhalogen, C₁-C₃ alkoxy, CN, NO₂, S(O)_(r)R¹⁵, COR¹³, CO₂R¹⁴ and phenyloptionally substituted with R²³ and R²⁴;

each R¹ and R² is independently selected from the group consisting ofC₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, halogen, CN, NO₂, OR¹⁶, S(O)_(r)R¹⁵,OS(O)₂R¹⁵, CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, SO₂NR⁹R¹⁰, SF₅, phenyloptionally substituted with R²³ and R²⁴ and benzyl optionallysubstituted with R²³ and R²⁴; or when m or n is 2, (R¹)₂ can be takentogether or (R²)₂ can be talen together as —OCH₂O—, —OCF₂O—, —OCH₂CH₂O—,—CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O—;

R³ is selected from the group consisting of J, C(R¹⁷)═N—O—R¹⁸, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl,C₂-C₆ alkoxylalkyl, C₃-C₈ alkoxycarbonylalkyl, CO₂R¹⁴, C(O)R¹³,C(O)NR⁹R¹⁰, C(S)NR⁹R¹⁰, C(S)R¹³, C(S)SR¹³, CN, and phenyl optionallysubstituted with R²³ and R²⁴; or R³ is C₂-C₆ epoxyalkyl optionallysubstituted with a group selected from C₁-C₃ alkyl, CN, C(O)R¹³, CO₂R¹⁴and phenyl optionally substituted with R²³ and R²⁴; or R³ is C₁-C₆ alkylsubstituted with a group selected from C(O)NR⁹R¹⁰, COR¹³, CO₂R¹⁴,S(O)_(m)R¹⁵, SCN, CN, C₁-C₂ haloalkoxy, SiR¹⁹R²⁰R²¹, NR⁹R¹⁰, NO₂,OC(O)R¹³, —P(O)(OR²²)₂, phenyl optionally substituted with R²³ and R²⁴,and J;

J is a nonaromatic or aromatic 5- or 6-membered heterocyclic ring,bonded through carbon or nitrogen, containing 1-4 heteroatomsindependently selected from the group consisting of 0-2 oxygen, 0-2sulfur and 0-4 nitrogen, optionally containing one carbonyl moiety andoptionally substituted with R²³ and R²⁴;

each R⁷ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₁-C₄ alkoxy, SO₂NR⁹R¹⁰, SO₂R¹³, COR⁹, CONR⁹R¹⁰, CO₂R¹³,phenyl optionally substituted with R²³ and R²⁴ or benzyl optionallysubstituted with R²³ and R²⁴;

each R⁸ is independently H, C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl, CO₂R¹³,SO₂R¹³, or benzyl optionally substituted with R²³ and R²⁴;

each R⁹ and each R¹¹ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl orphenyl optionally substituted with R²³ and R²⁴;

each R¹⁰ and each R¹² is independently H or C₁-C₄ alkyl; or

each pair of R⁹ and R¹⁰ when attached to the same atom or each pair ofR¹¹ and R¹² when attached to the same atom independently can be takentogether as —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂— or—CH₂CH₂OCH₂CH₂—, each of which is optionally and independentlysubstituted with 1 or 2 CH₃ groups;

each R¹³ and each R¹⁵ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkylor phenyl optionally substituted with R²³ and R²⁴;

each R¹⁴ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or benzyloptionally substituted with R²³ and R²⁴;

R¹⁶ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆haloalkenyl, C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyloptionally substituted with R²³ and R²⁴ and benzyl optionallysubstituted with R²³ and R²⁴;

R²¹ is selected from the group consisting of H, C₁-C₃ alkyl and phenyloptionally substituted with R²³ and R²⁴;

each R²³ is independently selected from the group consisting of 1-2halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyland C₁-C₂ haloalkylsulfonyl; and

each R²⁴ is independently selected from the group consisting of halogen,C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy.

Most preferred is the compound of Preferred 1:

7-Chloro-9,9α-dihydro-9α-propyl-N-[4-(trifluoromethoxy)phenyl]-1H-indeno[1,2-e]-1,2,4-triazine-3-Carboxamide.

This invention also relates to arthropodicidal compositions comprisingarthropodicidally effective amounts of the compounds of the inventionand at least one additional component selected from the group consistingof surfactants, solid diluents and liquid diluents. The preferredcompositions of the present invention are those which comprise the abovepreferred compounds.

This invention also relates to a method for controlling arthropodscomprising contacting the arthropods or their environment with anarthropodicidally effective amount of the compounds of the invention(e.g., as a composition described herein). The preferred methods of useare those involving the above preferred compounds.

The compounds of Formula I can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-12. Thedefinitions of A, E, G, W, X, Y, R², R³, Z, R⁴, R⁵, R⁶ and R⁷ in thecompounds of Formulae II-XVI below are as defined above in the Summaryof the Invention. Compounds of Formulae Ia-Ic are various subsets of thecompounds of Formula I, and all substituents for Formulae Ia-Ic are asdefined above for Formula I. In the Schemes, Rk is equivalent to R^(k)where k is a number from 1 to 7.

Transformations similar to those described in the Schemes have beenreported in the references associated with the Schemes. The reactionsmay be run at temperatures from −100 to 150° C. with temperatures from 0to 120° C. being preferred. Many solvents are acceptable includingethereal solvents such as diethyl ether, THF, dioxane, or glyme,halocarbon or hydrocarbon solvents such as chlorobenzene, CH₂Cl₂,hexanes, benzene, toluene or xylene, ketones such as acetone, and polaraprotic solvents such as acetonitrile, dimethylformamide,dimethylacetamide, and dimethylsulfoxide. In some instances aqueoussolvents or lower alcohols may be used. One skilled in the art willrecognize that the transformations may also be carried out usingcombinatorial chemistry techniques.

Compounds of Formula Ia (see Scheme 1 on previous page) can be preparedby reacting a compound of Formula II with a compound of Formula IIIusing procedures known to one skilled in the art (for Q is Cl, seeMarch, Advanced Organic Chemistry, 3^(rd) Edition, 1985, p. 370-376; forQ is OR, e.g., J. Chem. Soc., 1954, 1188; Synth. Commun., 1982, 12, 989;Tetrahedron Lett., 1971, 321).

Alternatively, compounds of Formula Ib can be prepared by condensing acompound of Formula IV with a compound of Formula V in the presence of abase.

Compounds of Formula IIa can be prepared by reacting a compound ofFormula VI with compound of Formula VII using procedures known to oneskilled in the art (e.g. Angew. Chem. int. Ed. Engl., 1981, 20, 296).

Compounds of Formula IIb (Q is OR) can be prepared by reacting acompound of Formula IV with a compound of Formula VIII using proceduresanalogous to those described for Scheme 2. One skilled in the art willrecognize that compounds of Formula IIb (Q is OR) can be converted intocompounds of Formula II wherein Q is Cl using known procedures (e.g.U.S. Pat. No. 5,708,170; March, Advanced Organic Chemistry, 3^(rd)Edition, pp. 334-338, 388).

Compounds of Formula X and IVa can be prepared from compounds of FormulaIX using procedures that are known to one skilled in the art (e.g., J.Org. Chem., 1988, 53, 2131; Tetrahedron Lett., 1991, 32, 5927; J. Am.Chem. Soc., 1986, 108, 6395).

Compounds of Formula IVb (X is O) can be prepared from compounds ofFormula XI using procedures that are known to one skilled in the art(e.g., Chem. Pharm. Bull., 1992, 40, 683). Compounds of Formula XI canbe prepared from compounds of Formula IX using procedures that are knownto one skilled in the art (for LG is Cl, Br, I, e.g., J. Am. Chem. Soc.,1959, 81, 1201; J. Org. Chem., 1968, 33, 419.1; and for LG is OMs(OSO₂CH₃), OTf, (OSO₂CF₃) and OTs (OSO₂C₆H₄CH₃), e.g., J. Org. Chem.,1985, 50, 5148; Tetrahedron Lett., 1992, 33, 7647; J. Org. Chem., 1982,47, 2487).

Compounds of Formula IVc (X is S) can be prepared by animation ofcompounds of Formula XII (X is S) using procedures that are known to oneskilled in the art (e.g., J. Org. Chem., 1972, 37, 3820; Synthesis,1991, 327; Synthetic Commun., 1986, 16, 899).

Compounds of Formula IVd (X is CR5R6) can be prepared from compounds ofFormula IX using procedures that are known to one skilled in the art(e.g., J. Am. Chem. Soc., 1942, 64, 45; Chem. Pharm. Bull., 1984, 32,4323).

Compounds of Formula VI can be prepared by condensation of compounds ofFormulae XIIa and XIII using procedures that are known to one skilled inthe art (e.g. March, Advanced Organic Chemistry, 3^(rd) Edition, pp.796-798).

Compounds of Formula XV can be prepared from compounds of Formula XIVusing procedures that are known to one skilled in the art (e.g., J.Chem. Soc. Chem. Commun., 1974, 826; Justus Liebigs Ann. Chem.,1949,562). Compounds of Formula V can be prepared using procedures describedfor the reaction in Scheme 10.

Compounds of Formula VII can be prepared from compounds of Formula XVIusing procedures that are known to one skilled in the art (e.g., J. OrgChem., 1973, 38, 1437; J. Heterocyclic Chem., 1988, 25, 651).

Compounds of Formula Ic, compounds of Formula I wherein Z is S, can beprepared by treating compounds of Formula Ia (I wherein Z is O) withthionating reagents such as P₂S₅ or Lawesson's reagent[2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide] asillustrated in Scheme 12 (see Bull. Soc. Chim. Belg., 1978, 87, 229; andTetrahedron Lett., 1983, 24, 3815).

Compounds of Formulae IX and XII can be prepared using proceduresdescribed in U.S. Pat. No. 5,708,170.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula I may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula I. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula I.

One skilled in the art will also recognize that compounds of Formula Iand the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except for chromatographic solventmixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; ¹⁹F NMR spectra are reported in ppm relative toCFCl₃; s is singlet, d is doublet, t is triplet, q is quartet, m ismultiplet, dd is doublet of doublets, dt is doublet of triplets, and brs is broad singlet.

EXAMPLE 1

Step A: Preparation of 1-(4-Trifluoromethyl-phenyl)-pentan-1-one

To a suspension of copper bromide-dimethylsulfide complex (11.0 g, 53.5mmol) in 200 mL ether at −78° C. was added 65 mL of n-BuLi (1.6M, 104.0mmol) dropwise. The mixture was stirred at −78° C. for 45 min, warmed to−40° C. for 10 min and then re-cooled to −78° C. A solution of4-trifluoromethylbenzoyl chloride (10.0 g, 48.0 mmol) in 50 mL ether wasadded dropwise at −78° C. After addition was complete, the reaction wasstirred at −78° C. for 30 min, quenched with saturated (sat.) ammoniumchloride and allowed to warm to room temperature (RT). The mixture waspoured into ether containing ca 10 mL methanol and was washed with amixture of ammonium chloride/ammonium hydroxide. The combined aqueouslayers were extracted with ether. The combined ether layers were dried(MgSO₄), filtered and concentrated to give 11.0 g of a solid. ¹H NMR(CDCl₃) δ 8.05 (d,2H), 7.72 (d,2H), 2.99 (t,2H), 1.80-1.67 (m,2H),1.50-1.35 (m,2H), 0.96 (t,3H). ¹⁹F NMR (CDCl₃) δ −63.13.

Step B: Preparation of 1-(4-Trifluoromethyl-phenyl)-2-propyl-propenone

To a solution of the product from Step A (10.6 g, 46.1 mmol) in 80 mLmethanol was added 13.8 mL aqueous formaldehyde (37%, 183.5 mmol),piperidine (0.5 mL, 5.0 mmol) and acetic acid (0.5 mL, 8.7 mmol). Themixture was heated under reflux for 62 h, cooled to RT and concentratedin vacuo. The residue was dissolved in ether and dilute aq. NaCl,extracted with ether, dried (MgSO₄) and concentrated to give 10.6 g ofan oil. ¹H NMR (CDCl₃) δ 7.82 (d,2H0, 7.70 (d,2H), 5.92 (s,1H), 5.61(s,1H), 2.46 (t,2H), 1.60-1.45 (m,2H), 0.98 (t,3H). ¹⁹F NMR (CDCl₃) 67−63.53.

Step C: Preparation of 2-propyl-5-trifluoromethyl-indan-1-one

The product of Step C (10.5 g, 43.2 mmol) was added dropwise to 50 g oftrifluoromethanesulfonic acid cooled to 0° C. The reaction was stirredat 0° C. for 3 h then allowed to warm to RT. After 16 h, the mixture waspoured into 250 mL and extracted (3×) with ethyl acetate. The combinedorganic layers were washed with water (1×), sat. sodium bicarbonatesolution (2×), dried (MgSO₄), filtered and concentrated. The residue waspurifed by chromatography on silica gel eluting with 5% ethylacetate/hexane to afford 8.8 g of a yellow oil. ¹H NMR (CDCl₃) δ 7.85(d,1H), 7.73 (s,1H), 7.60 (d,1H), 3.40 (dd,1H), 2.90 (dd,1H), 2.80-2.70(m,1H), 1.60-1.40 (m,3H), 0.97 (t,3H). ¹⁹F NMR (CDCl₃) δ −63.36.

Step D: Preparation of bis(1,1-dimethylethyl)1-[2.3-dihydro-1-oxo-2-propyl-5-(trifluoromethyl)-1H-inden-2-yl]-1.2-hydrazinedicarboxylicacid

To a solution of diisopropropylamine (1.3 mL, 9.1 mmol) in 30 mLtetrahydrofuran cooled to −78° C. was added 6.0 mL n-BuLi (1.6M, 9.5mmol). The mixture was allowed to warm to −20° C. over 20 min, thenre-cooled to −78° C. A solution of the product from Step C (2.0 g, 8.3mmol) in 15 mL tetrahydrofuran was added dropwise. After 30 min, asolution of di-tert-butylazodicarboxylate (2.1 g, 9.1 mmol) in 20 mLtetrahydrofuran was added dropwise. The reaction was allowed to slowlywarm to RT and stirred overnight. Water was added and the mixture wasextracted with ethyl acetate, dried (MgSO₄), filtered and concentrated.The residue was purified by chromatography on silica gel eluting with10% ethyl acetate/hexane to afford 2.92 g of a white solid, m.p.135-137° C.

Step E: Preparation of methyl9.9α-dihydro-9α-propyl-7-(trifluoromethyl)-1H-indeno[1,2-e]-1,2,4-triazine-3-Carboxylate

To a solution of the product from Step D (1.5 g, 3.2 mmol) in 5 mLdichloromethane and 1 mL toluene was added 2 mL trifluoroacetic acid.After 4 h, the solvent was removed in vacuo. The residue was suspendedin hexane and the solvent was removed (2×). A solution of the residuedissolved in 20 mL methanol was treated with ethylcarbomethoxyformimidate hydrochloride (0.6 g, 3.5 mmol), preparedaccording to the procedure in J. Heterocyclic Chem. 1988, 25, 651. After24 h, solid sodium bicarbonate (ca. 1 g) was added. The mixture waspoured into water, extracted with ethyl acetate, dried (MgSO₄), filteredand concentrated. The solids were triturated with hexanes and dried invacuo to provide 0.5 g of a yellow solid, m.p. 141-142° C.

Step F: Preparation of9,9α-dihydro-9α-propyl-N-[4-(trifluoromethoxy)phenyl]-7-(trifluoromethyl)-1H-indeno[1,2-e]-1,2,4-triazine-3-carboxamide

To a solution of 4-trifluoromethoxyaniline (0.68 g, 3.9 mmol) dissolvedin 10 mL tetrahydrofuran was added 1.3 mL of methylmagnesium chloride(3.0M in tetrahydrofuran, 3.9 mmol). After 10 min, the mixture was addedto a solution of the product from Step E (0.20 g, 0.59 mmol) in 7 mLtetrahydrofuran in one portion. After 16 h, ether and 1N HCl was added.The organic layer was washed with 1N HCl (2×), sat. sodium bicarbonatesolution (1×), dried (MgSO₄), filtered and concentrated. The residue wastaken up in ether. Solids formed on sitting. The solids were washed withether and hexane and dried in vacuo to afford 0.11 g of a solid, m.p.192-194° C. A second crop of 0.18 g of product was also isolated.

EXAMPLE 2 Preparation ofN-(4-bromophenyl)-9,9α-dihydro-9α-propyl-7-(trifluoromethyl)-1H-indeno[1,2,-e]-1.2,4-triazine-3-carboxamide

To a solution of 4-bromoaniline (0.67 g, 3.9 mmol) dissolved in 10 mLtetrahydrofuran was added 1.3 mL of methylmagnesium chloride (3.0M intetrahydrofuran, 3.9 mmol). After 10 min, the mixture was added to asolution of the product from Ex. 1, Step E (0.2 g, 0.59 mmol) in 7 mLtetrahydrofuran in one portion. After 16 h, ether and 1N HCl was added.The organic layer was washed with 1N HCl (2×), sat. sodium bicarbonatesolution (1×), dried (MgSO₄), filtered and concentrated. The residue wastaken up in ether. Solids formed on sitting. The solids were washed withether and hexane and dried in vacuo to afford 0.16 g of a solid, m.p.198-199° C.

By the procedures described herein together with methods known in theart, the following compounds of Tables 1 to 3 can be prepared. Thefollowing abbreviations are used in the Tables: t is tertiary, s issecondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl,Pr is propyl, i-Pr is isopropyl, Bu is butyl, Ph is phenyl, OMe ismethoxy, OEt is ethoxy and CN is cyano.

TABLE 1

when AE is listed as H, H, there is no link between the rings at AE AE(R¹)_(m) (R²)_(n) R³ R⁷ CH₂ 4-OCF₃ 4-Cl Me H CH₂ 4-OCF₃ 4-Cl Et H CH₂4-OCF₃ 4-Cl n-Pr H CH₂ 4-OCF₃ 4-Cl i-Pr H CH₂ 4-OCF₃ 4-Cl n-Bu H CH₂4-OCF₃ 4-Cl i-Bu H CH₂ 4-OCF₃ 4-Cl c-Pr H CH₂ 4-OCF₃ 4-Cl Ph H CH₂4-OCF₃ 4-Cl 4-Cl—Ph H CH₂ 4-OCF₃ 4-Cl 4-F—Ph H CH₂ 4-OCF₃ 4-Cl 4-CN—Ph HCH₂ 4-OCF₃ 4-Cl CO₂Me H CH₂ 4-CF₃ 4-Cl Me H CH₂ 4-CF₃ 4-Cl Et H CH₂4-CF₃ 4-Cl n-Pr H CH₂ 4-CF₃ 4-Cl i-Pr H CH₂ 4-CF₃ 4-Cl n-Bu H CH₂ 4-CF₃4-Cl i-Bu H CH₂ 4-CF₃ 4-Cl c-Pr H CH₂ 4-CF₃ 4-Cl Ph H CH₂ 4-CF₃ 4-Cl4-Cl—Ph H CH₂ 4-CF₃ 4-Cl 4-F—Ph H CH₂ 4-CF₃ 4-Cl 4-CN—Ph H CH₂ 4-CF₃4-Cl CO₂Me H CH₂ 4-OCF₃ 4-CF₃ Me H CH₂ 4-OCF₃ 4-CF₃ Et H CH₂ 4-OCF₃4-CF₃ n-Pr H CH₂ 4-OCF₃ 4-CF₃ i-Pr H CH₂ 4-OCF₃ 4-CF₃ n-Bu H CH₂ 4-OCF₃4-CF₃ i-Bu H CH₂ 4-OCF₃ 4-CF₃ c-Pr H CH₂ 4-OCF₃ 4-CF₃ Ph H CH₂ 4-OCF₃4-CF₃ 4-Cl—Ph H CH₂ 4-OCF₃ 4-CF₃ 4-F—Ph H CH₂ 4-OCF₃ 4-CF₃ 4-CN—Ph H CH₂4-OCF₃ 4-CF₃ CO₂Me H CH₂ 4-CF₃ 4-CF₃ Me H CH₂ 4-CF₃ 4-CF₃ Et H CH₂ 4-CF₃4-CF₃ n-Pr H CH₂ 4-CF₃ 4-CF₃ i-Pr H CH₂ 4-CF₃ 4-CF₃ n-Bu H CH₂ 4-CF₃4-CF₃ i-Bu H CH₂ 4-CF₃ 4-CF₃ c-Pr H CH₂ 4-CF₃ 4-CF₃ Ph H CH₂ 4-CF₃ 4-CF₃4-Cl—Ph H CH₂ 4-CF₃ 4-CF₃ 4-F—Ph H CH₂ 4-CF₃ 4-CF₃ 4-CN—Ph H CH₂ 4-CF₃4-CF₃ CO₂Me H CH₂ 4-OCF₃ 4-F Me H CH₂ 4-OCF₃ 4-F Et H CH₂ 4-OCF₃ 4-Fn-Pr H CH₂ 4-OCF₃ 4-F i-Pr H CH₂ 4-OCF₃ 4-F n-Bu H CH₂ 4-OCF₃ 4-F i-Bu HCH₂ 4-OCF₃ 4-F c-Pr H CH₂ 4-OCF₃ 4-F Ph H CH₂ 4-OCF₃ 4-F 4-Cl—Ph H CH₂4-OCF₃ 4-F 4-F—Ph H CH₂ 4-OCF₃ 4-F 4-CN—Ph H CH₂ 4-OCF₃ 4-F CO₂Me H CH₂4-OCF₃ 3-F Me H CH₂ 4-OCF₃ 3-F Et H CH₂ 4-OCF₃ 3-F n-Pr H CH₂ 4-OCF₃ 3-Fi-Pr H CH₂ 4-OCF₃ 3-F n-Bu H CH₂ 4-OCF₃ 3-F i-Bu H CH₂ 4-OCF₃ 3-F c-Pr HCH₂ 4-OCF₃ 3-F Ph H CH₂ 4-OCF₃ 3-F 4-Cl—Ph H CH₂ 4-OCF₃ 3-F 4-F—Ph H CH₂4-OCF₃ 3-F 4-CN—Ph H CH₂ 4-OCF₃ 3-F CO₂Me H CH₂ 4-OCF₃ 3-Cl Me H CH₂4-OCF₃ 3-Cl Et H CH₂ 4-OCF₃ 3-Cl n-Pr H CH₂ 4-OCF₃ 3-Cl i-Pr H CH₂4-OCF₃ 3-Cl n-Bu H CH₂ 4-OCF₃ 3-Cl i-Bu H CH₂ 4-OCF₃ 3-Cl c-Pr H CH₂4-OCF₃ 3-Cl Ph H CH₂ 4-OCF₃ 3-Cl 4-Cl—Ph H CH₂ 4-OCF₃ 3-Cl 4-F—Ph H CH₂4-OCF₃ 3-Cl 4-CN—Ph H CH₂ 4-OCF₃ 3-Cl CO₂Me H CH₂ 4-OCF₃ 4-Br Me H CH₂4-OCF₃ 4-Br Et H CH₂ 4-OCF₃ 4-Br n-Pr H CH₂ 4-OCF₃ 4-Br i-Pr H CH₂4-OCF₃ 4-Br n-Bu H CH₂ 4-OCF₃ 4-Br i-Bu H CH₂ 4-OCF₃ 4-Br c-Pr H CH₂4-OCF₃ 4-Br Ph H CH₂ 4-OCF₃ 4-Br 4-Cl—Ph H CH₂ 4-OCF₃ 4-Br 4-F—Ph H CH₂4-OCF₃ 4-Br 4-CN—Ph H CH₂ 4-OCF₃ 4-Br CO₂Me H O 4-OCF₃ 4-Cl Me H O4-OCF₃ 4-Cl Et H O 4-OCF₃ 4-Cl n-Pr H O 4-OCF₃ 4-Cl i-Pr H O 4-OCF₃ 4-Cln-Bu H O 4-OCF₃ 4-Cl i-Bu H O 4-OCF₃ 4-Cl c-Pr H O 4-OCF₃ 4-Cl Ph H O4-OCF₃ 4-Cl 4-Cl—Ph H O 4-OCF₃ 4-Cl 4-F—Ph H O 4-OCF₃ 4-Cl 4-CN—Ph H O4-OCF₃ 4-Cl CO₂Me H O 4-CF₃ 4-Cl Me H O 4-CF₃ 4-Cl Et H O 4-CF₃ 4-Cln-Pr H O 4-CF₃ 4-Cl i-Pr H O 4-CF₃ 4-Cl n-Bu H O 4-CF₃ 4-Cl i-Bu H O4-CF₃ 4-Cl c-Pr H O 4-CF₃ 4-Cl Ph H O 4-CF₃ 4-Cl 4-Cl—Ph H O 4-CF₃ 4-Cl4-F—Ph H O 4-CF₃ 4-Cl 4-CN—Ph H O 4-CF₃ 4-Cl CO₂Me H O 4-OCF₃ 4-CF₃ Me HO 4-OCF₃ 4-CF₃ Et H O 4-OCF₃ 4-CF₃ n-Pr H O 4-OCF₃ 4-CF₃ i-Pr H O 4-OCF₃4-CF₃ n-Bu H O 4-OCF₃ 4-CF₃ i-Bu H O 4-OCF₃ 4-CF₃ c-Pr H O 4-OCF₃ 4-CF₃Ph H O 4-OCF₃ 4-CF₃ 4-Cl—Ph H O 4-OCF₃ 4-CF₃ 4-F—Ph H O 4-OCF₃ 4-CF₃4-CN—Ph H O 4-OCF₃ 4-CF₃ CO₂Me H O 4-CF₃ 4-CF₃ Me H O 4-CF₃ 4-CF₃ Et H O4-CF₃ 4-CF₃ n-Pr H O 4-CF₃ 4-CF₃ i-Pr H O 4-CF₃ 4-CF₃ n-Bu H O 4-CF₃4-CF₃ i-Bu H O 4-CF₃ 4-CF₃ c-Pr H O 4-CF₃ 4-CF₃ Ph H O 4-CF₃ 4-CF₃4-Cl—Ph H O 4-CF₃ 4-CF₃ 4-F—Ph H O 4-CF₃ 4-CF₃ 4-CN—Ph H O 4-CF₃ 4-CF₃CO₂Me H CH₂ 4-OCF₃ 4-CF₃ Me H CH₂ 4-OCF₃ 4-CF₃ Et H H, H 4-OCF₃ 5-CF₃n-Pr H H, H 4-OCF₃ 5-CF₃ i-Pr H H, H 4-OCF₃ 5-CF₃ n-Bu H H, H 4-OCF₃5-CF₃ i-Bu H H, H 4-OCF₃ 5-CF₃ c-Pr H H, H 4-OCF₃ 5-CF₃ Ph H H, H 4-OCF₃5-CF₃ 4-Cl—Ph H H, H 4-OCF₃ 5-CF₃ 4-F—Ph H H, H 4-OCF₃ 5-CF₃ 4-CN—Ph HH, H 4-OCF₃ 5-CF₃ CO₂Me H H, H 4-CF₃ 5-CF₃ Me H H, H 4-CF₃ 5-CF₃ Et H H,H 4-CF₃ 5-CF₃ n-Pr H H, H 4-CF₃ 5-CF₃ i-Pr H H, H 4-CF₃ 5-CF₃ n-Bu H H,H 4-CF₃ 5-CF₃ i-Bu H H, H 4-CF₃ 5-CF₃ c-Pr H H, H 4-CF₃ 5-CF₃ Ph H H, H4-CF₃ 5-CF₃ 4-Cl—Ph H H, H 4-CF₃ 5-CF₃ 4-F—Ph H H, H 4-CF₃ 5-CF₃ 4-CN—PhH H, H 4-CF₃ 5-CF₃ CO₂Me H CH₂ 4-OCF₃ 4-CF₃ n-Pr Me CF₂ 4-OCF₃ 4-CF₃n-Pr Et CF₂ 4-OCF₃ 4-CF₃ n-Pr Allyl CH₂ 4-OCF₃ 4-CF₃ n-Pr Propargyl CH₂4-OCF₃ 4-CF₃ n-Pr Acetyl CH₂ 4-OCF₃ 4-CF₃ n-Pr Propionyl CH₂ 4-OCF₃4-CF₃ n-Pr Butyryl CH₂ 4-OCF₃ 4-CF₃ n-Pr Benzoyl CH₂ 4-OCF₃ 4-CF₃ n-PrCO₂Me CH₂ 4-OCF₃ 4-CF₃ n-Pr CO₂Et CH₂ 4-OCF₃ 4-CF₃ n-Pr COCO₂Me CH₂4-OCF₃ 4-CF₃ n-Pr COCO₂Et CH₂ 4-OCF₃ 4-CF₃ n-Pr Benzyl CH₂ 4-OCF₃ 4-CF₃n-Pr CO₂Ph CH₂ 4-OCF₃ 4-CF₃ n-Pr CO-c-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CO-i-PrCH₂ 4-OCF₃ 4-CF₃ n-Pr CONMe₂ CH₂ 4-OCF₃ 4-CF₃ n-Pr CONHMe CH₂ 4-OCF₃4-Cl n-Pr Me CH₂ 4-OCF₃ 4-Cl n-Pr Et CH₂ 4-OCF₃ 4-Cl n-Pr Allyl CH₂4-OCF₃ 4-Cl n-Pr Propargyl CH₂ 4-OCF₃ 4-Cl n-Pr Acetyl CH₂ 4-OCF₃ 4-Cln-Pr Propionyl CH₂ 4-OCF₃ 4-Cl n-Pr Butyryl CH₂ 4-OCF₃ 4-Cl n-Pr BenzoylCH₂ 4-OCF₃ 4-Cl n-Pr CO₂Me CH₂ 4-OCF₃ 4-Cl n-Pr CO₂Et CH₂ 4-OCF₃ 4-Cln-Pr COCO₂Me CH₂ 4-OCF₃ 4-Cl n-Pr COCO₂Et CH₂ 4-OCF₃ 4-Cl n-Pr BenzylCH₂ 4-OCF₃ 4-Cl n-Pr CO₂Ph CH₂ 4-OCF₃ 4-Cl n-Pr CO-c-Pr CH₂ 4-OCF₃ 4-Cln-Pr CO-i-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CONMe₂ CH₂ 4-OCF₃ 4-Cl n-Pr CONHMe CH₂4-Br 4-Cl Me H CH₂ 4-Br 4-Cl Et H CH₂ 4-Br 4-Cl n-Pr H CH₂ 4-Br 4-Cli-Pr H CH₂ 4-Br 4-Cl n-Bu H CH₂ 4-Br 4-Cl i-Bu H CH₂ 4-Br 4-Cl c-Pr HCH₂ 4-Br 4-Cl Ph H CH₂ 4-Br 4-Cl 4-Cl—Ph H CH₂ 4-Br 4-Cl 4-F—Ph H CH₂4-Br 4-Cl 4-CN—Ph H CH₂ 4-Br 4-Cl CO₂Me H OCH₂ 4-OCF₃ 3-Cl n-Pr H CH₂O4-OCF₃ 3-Cl n-Pr H S 4-OCF₃ 4-Cl n-Pr H NH 4-OCF₃ 4-Cl n-Pr H CH₂CH₂4-OCF₃ 3-Cl n-Pr H NHCH₂ 4-OCF₃ 3-Cl n-Pr H CH₂NH 4-OCF₃ 3-Cl n-Pr H

TABLE 2

when AE is listed as H, H, there is no link between the rings at AE AE(R¹)_(m) (R²)_(n) R³ CH₂ 4-OCF₃ 4-Cl Me CH₂ 4-OCF₃ 4-Cl Et CH₂ 4-OCF₃4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl i-Pr CH₂ 4-OCF₃ 4-Cl n-Bu CH₂ 4-OCF₃ 4-Cl i-BuCH₂ 4-OCF₃ 4-Cl c-Pr CH₂ 4-OCF₃ 4-Cl Ph CH₂ 4-OCF₃ 4-Cl 4-Cl—Ph CH₂4-OCF₃ 4-Cl 4-F—Ph CH₂ 4-OCF₃ 4-Cl 4-CN—Ph CH₂ 4-OCF₃ 4-Cl CO₂Me CH₂4-CF₃ 4-Cl Me CH₂ 4-CF₃ 4-Cl Et CH₂ 4-CF₃ 4-Cl n-Pr CH₂ 4-CF₃ 4-Cl i-PrCH₂ 4-CF₃ 4-Cl n-Bu CH₂ 4-CF₃ 4-Cl i-Bu CH₂ 4-CF₃ 4-Cl c-Pr CH₂ 4-CF₃4-Cl Ph CH₂ 4-CF₃ 4-Cl 4-Cl—Ph CH₂ 4-CF₃ 4-Cl 4-F—Ph CH₂ 4-CF₃ 4-Cl4-CN—Ph CH₂ 4-CF₃ 4-Cl CO₂Me CH₂ 4-OCF₃ 4-CF₃ Me CH₂ 4-OCF₃ 4-CF₃ Et CH₂4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ i-Pr CH₂ 4-OCF₃ 4-CF₃ n-Bu CH₂ 4-OCF₃4-CF₃ i-Bu CH₂ 4-OCF₃ 4-CF₃ c-Pr CH₂ 4-OCF₃ 4-CF₃ Ph CH₂ 4-OCF₃ 4-CF₃4-Cl—Ph CH₂ 4-OCF₃ 4-CF₃ 4-F—Ph CH₂ 4-CCF₃ 4-CF₃ 4-CN—Ph CH₂ 4-OCF₃4-CF₃ CO₂Me CH₂ 4-CF₃ 4-CF₃ Me CH₂ 4-CF₃ 4-CF₃ Et CH₂ 4-CF₃ 4-CF₃ n-PrCH₂ 4-CF₃ 4-CF₃ i-Pr CH₂ 4-CF₃ 4-CF₃ n-Bu CH₂ 4-CF₃ 4-CF₃ i-Bu CH₂ 4-CF₃4-CF₃ c-Pr CH₂ 4-CF₃ 4-CF₃ Ph CH₂ 4-CF₃ 4-CF₃ 4-Cl—Ph CH₂ 4-CF₃ 4-CF₃4-F—Ph CH₂ 4-CF₃ 4-CF₃ 4-CN—Ph CH₂ 4-CF₃ 4-CF₃ CO₂Me CH₂ 4-OCF₃ 4-F MeCH₂ 4-OCF₃ 4-F Et CH₂ 4-OCF₃ 4-F n-Pr CH₂ 4-OCF₃ 4-F i-Pr CH₂ 4-OCF₃ 4-Fn-Bu CH₂ 4-OCF₃ 4-F i-Bu CH₂ 4-OCF₃ 4-F c-Pr CH₂ 4-OCF₃ 4-F Ph CH₂4-OCF₃ 4-F 4-Cl—Ph CH₂ 4-OCF₃ 4-F 4-F—Ph CH₂ 4-OCF₃ 4-F 4-CN—Ph CH₂4-OCF₃ 4-F CO₂Me CH₂ 4-OCF₃ 3-F Me CH₂ 4-OCF₃ 3-F Et CH₂ 4-OCF₃ 3-F n-PrCH₂ 4-OCF₃ 3-F i-Pr CH₂ 4-OCF₃ 3-F n-Bu CH₂ 4-OCF₃ 3-F i-Bu CH₂ 4-OCF₃3-F c-Pr CH₂ 4-OCF₃ 3-F Ph CH₂ 4-OCF₃ 3-F 4-Cl—Ph CH₂ 4-OCF₃ 3-F 4-F—PhCH₂ 4-OCF₃ 3-F 4-CN—Ph CH₂ 4-OCF₃ 3-F CO₂Me CH₂ 4-OCF₃ 3-Cl Me CH₂4-OCF₃ 3-Cl Et CH₂ 4-OCF₃ 3-Cl n-Pr CH₂ 4-OCF₃ 3-Cl i-Pr CH₂ 4-OCF₃ 3-Cln-Bu CH₂ 4-OCF₃ 3-Cl i-Bu CH₂ 4-OCF₃ 3-Cl c-Pr CH₂ 4-OCF₃ 3-Cl Ph CH₂4-OCF₃ 3-Cl 4-Cl—Ph CH₂ 4-OCF₃ 3-Cl 4-F—Ph CH₂ 4-OCF₃ 3-Cl 4-CN—Ph CH₂4-OCF₃ 3-Cl CO₂Me CH₂ 4-OCF₃ 4-Br Me CH₂ 4-OCF₃ 4-Br Et CH₂ 4-OCF₃ 4-Brn-Pr CH₂ 4-OCF₃ 4-Br i-Pr CH₂ 4-OCF₃ 4-Br n-Bu CH₂ 4-OCF₃ 4-Br i-Bu CH₂4-OCF₃ 4-Br c-Pr CH₂ 4-OCF₃ 4-Br Ph CH₂ 4-OCF₃ 4-Br 4-Cl—Ph CH₂ 4-OCF₃4-Br 4-F—Ph CH₂ 4-OCF₃ 4-Br 4-CN—Ph CH₂ 4-OCF₃ 4-Br CO₂Me O 4-OCF₃ 4-ClMe O 4-OCF₃ 4-Cl Et O 4-OCF₃ 4-Cl n-Pr O 4-OCF₃ 4-Cl i-Pr O 4-OCF₃ 4-Cln-Bu O 4-OCF₃ 4-Cl i-Bu O 4-OCF₃ 4-Cl c-Pr O 4-OCF₃ 4-Cl Ph O 4-OCF₃4-Cl 4-Cl—Ph O 4-OCF₃ 4-Cl 4-F—Ph O 4-OCF₃ 4-Cl 4-CN—Ph O 4-OCF₃ 4-ClCO₂Me O 4-CF₃ 4-Cl Me O 4-CF₃ 4-Cl Et O 4-CF₃ 4-Cl n-Pr O 4-CF₃ 4-Cli-Pr O 4-CF₃ 4-Cl n-Bu O 4-CF₃ 4-Cl i-Bu O 4-CF₃ 4-Cl c-Pr O 4-CF₃ 4-ClPh O 4-CF₃ 4-Cl 4-Cl—Ph O 4-CF₃ 4-Cl 4-F—Ph O 4-CF₃ 4-Cl 4-CN—Ph O 4-CF₃4-Cl CO₂Me O 4-OCF₃ 4-CF₃ Me O 4-OCF₃ 4-CF₃ Et O 4-OCF₃ 4-CF₃ n-Pr O4-OCF₃ 4-CF₃ i-Pr O 4-OCF₃ 4-CF₃ n-Bu O 4-OCF₃ 4-CF₃ i-Bu O 4-OCF₃ 4-CF₃c-Pr O 4-OCF₃ 4-CF₃ Ph O 4-OCF₃ 4-CF₃ 4-Cl—Ph O 4-OCF₃ 4-CF₃ 4-F—Ph O4-OCF₃ 4-CF₃ 4-CN—Ph O 4-OCF₃ 4-CF₃ CO₂Me O 4-CF₃ 4-CF₃ Me O 4-CF₃ 4-CF₃Et O 4-CF₃ 4-CF₃ n-Pr O 4-CF₃ 4-CF₃ i-Pr O 4-CF₃ 4-CF₃ n-Bu O 4-CF₃4-CF₃ i-Bu O 4-CF₃ 4-CF₃ c-Pr O 4-CF₃ 4-CF₃ Ph O 4-CF₃ 4-CF₃ 4-Cl—Ph O4-CF₃ 4-CF₃ 4-F—Ph O 4-CF₃ 4-CF₃ 4-CN—Ph O 4-CF₃ 4-CF₃ CO₂Me CH₂ 4-OCF₃4-CF₃ Me CH₂ 4-OCF₃ 4-CF₃ Et H, H 4-OCF₃ 5-CF₃ n-Pr H, H 4-OCF₃ S-CF₃i-Pr H, H 4-OCF₃ 5-CF₃ n-Bu H, H 4-OCF₃ 5-CF₃ i-Bu H, H 4-OCF₃ 5-CF₃c-Pr H, H 4-OCF₃ 5-CF₃ Ph H, H 4-OCF₃ 5-CF₃ 4-Cl—Ph H, H 4-OCF₃ 5-CF₃4-F—Ph H, H 4-OCF₃ 5-CF₃ 4-CN—Ph H, H 4-OCF₃ 5-CF₃ CO₂Me H, H 4-CF₃5-CF₃ Me H, H 4-CF₃ 5-CF₃ Et H, H 4-CF₃ 5-CF₃ n-Pr H, H 4-CF₃ 5-CF₃ i-PrH, H 4-CF₃ 5-CF₃ n-Bu H, H 4-CF₃ 5-CF₃ i-Bu H, H 4-CF₃ 5-CF₃ c-Pr H, H4-CF₃ 5-CF₃ Ph H, H 4-CF₃ 5-CF₃ 4-Cl—Ph H, H 4-CF₃ 5-CF₃ 4-F—Ph H, H4-CF₃ 5-CF₃ 4-CN—Ph H, H 4-CF₃ 5-CF₃ CO₂Me CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-PrCH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr CH₂ 4-OCF₃4-CF₃ n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cln-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-PrCH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂4-OCF₃ 4-Cl n-Pr CH₂ 4-OCF₃ 4-Cl n-Pr CH₂ 4-Br 4-Cl Me CH₂ 4-Br 4-Cl EtCH₂ 4-Br 4-Cl n-Pr CH₂ 4-Br 4-Cl i-Pr CH₂ 4-Br 4-Cl n-Bu CH₂ 4-Br 4-Cli-Bu CH₂ 4-Br 4-Cl c-Pr CH₂ 4-Br 4-Cl Ph CH₂ 4-Br 4-Cl 4-Cl—Ph CH₂ 4-Br4-Cl 4-F—Ph CH₂ 4-Br 4-Cl 4-CN—Ph CH₂ 4-Br 4-Cl CO₂Me OCH₂ 4-OCF₃ 3-Cln-Pr CH₂O 4-OCF₃ 3-Cl n-Pr S 4-OCF₃ 4-Cl n-Pr NH 4-OCF₃ 4-Cl n-Pr CH₂CH₂4-OCF₃ 3-Cl n-Pr NHCH₂ 4-OCF₃ 3-Cl n-Pr CH₂NH 4-OCF₃ 3-Cl n-Pr

TABLE 3

when AE is listed as H, H, there is no link between the rings at AE AE(R¹)_(m) (R²)_(n) R³ R⁶ CH₂ 4-OCF₃ 4-Cl Me H CH₂ 4-OCF₃ 4-Cl Et H CH₂4-OCF₃ 4-Cl n-Pr H CH₂ 4-OCF₃ 4-Cl i-Pr H CH₂ 4-OCF₃ 4-Cl n-Bu H CH₂4-OCF₃ 4-Cl i-Bu H CH₂ 4-OCF₃ 4-Cl c-Pr H CH₂ 4-OCF₃ 4-Cl Ph H CH₂4-OCF₃ 4-Cl 4-Cl—Ph H CH₂ 4-OCF₃ 4-Cl 4-F—Ph H CH₂ 4-OCF₃ 4-Cl 4-CN—Ph HCH₂ 4-OCF₃ 4-Cl CO₂Me H CH₂ 4-CF₃ 4-Cl Me H CH₂ 4-CF₃ 4-Cl Et H CH₂4-CF₃ 4-Cl n-Pr H CH₂ 4-CF₃ 4-Cl i-Pr H CH₂ 4-CF₃ 4-Cl n-Bu H CH₂ 4-CF₃4-Cl i-Bu H CH₂ 4-CF₃ 4-Cl c-Pr H CH₂ 4-CF₃ 4-Cl Ph H CH₂ 4-CF₃ 4-Cl4-Cl—Ph H CH₂ 4-CF₃ 4-Cl 4-F—Ph H CH₂ 4-CF₃ 4-Cl 4-CN—Ph H CH₂ 4-CF₃4-Cl CO₂Me H CH₂ 4-OCF₃ 4-CF₃ Me H CH₂ 4-OCF₃ 4-CF₃ Et H CH₂ 4-OCF₃4-CF₃ n-Pr H CH₂ 4-OCF₃ 4-CF₃ i-Pr H CH₂ 4-OCF₃ 4-CF₃ n-Bu H CH₂ 4-OCF₃4-CF₃ i-Bu H CH₂ 4-OCF₃ 4-CF₃ c-Pr H CH₂ 4-OCF₃ 4-CF₃ Ph H CH₂ 4-OCF₃4-CF₃ 4-Cl—Ph H CH₂ 4-OCF₃ 4-CF₃ 4-F—Ph H CH₂ 4-OCF₃ 4-CF₃ 4-CN—Ph H CH₂4-OCF₃ 4-CF₃ CO₂Me H CH₂ 4-CF₃ 4-CF₃ Me H CH₂ 4-CF₃ 4-CF₃ Et H CH₂ 4-CF₃4-CF₃ n-Pr H CH₂ 4-CF₃ 4-CF₃ i-Pr H CH₂ 4-CF₃ 4-CF₃ n-Bu H CH₂ 4-CF₃4-CF₃ i-Bu H CH₂ 4-CF₃ 4-CF₃ c-Pr H CH₂ 4-CF₃ 4-CF₃ Ph H CH₂ 4-CF₃ 4-CF₃4-Cl—Ph H CH₂ 4-CF₃ 4-CF₃ 4-F—Ph H CH₂ 4-CF₃ 4-CF₃ 4-CN—Ph H CH₂ 4-CF₃4-CF₃ CO₂Me H CH₂ 4-OCF₃ 4-F Me H CH₂ 4-OCF₃ 4-F Et H CH₂ 4-OCF₃ 4-Fn-Pr H CH₂ 4-OCF₃ 4-F i-Pr H CH₂ 4-OCF₃ 4-F n-Bu H CH₂ 4-OCF₃ 4-F i-Bu HCH₂ 4-OCF₃ 4-F c-Pr H CH₂ 4-OCF₃ 4-F Ph H CH₂ 4-OCF₃ 4-F 4-Cl—Ph H CH₂4-OCF₃ 4-F 4-F—Ph H CH₂ 4-OCF₃ 4-F 4-CN—Ph H CH₂ 4-OCF₃ 4-F CO₂Me H CH₂4-OCF₃ 3-F Me H CH₂ 4-OCF₃ 3-F Et H CH₂ 4-OCF₃ 3-F n-Pr H CH₂ 4-OCF₃ 3-Fi-Pr H CH₂ 4-OCF₃ 3-F n-Bu H CH₂ 4-OCF₃ 3-F i-Bu H CH₂ 4-OCF₃ 3-F c-Pr HCH₂ 4-OCF₃ 3-F Ph H CH₂ 4-OCF₃ 3-F 4-Cl—Ph H CH₂ 4-OCF₃ 3-F 4-F—Ph H CH₂4-OCF₃ 3-F 4-CN—Ph H CH₂ 4-OCF₃ 3-F CO₂Me H CH₂ 4-OCF₃ 3-Cl Me H CH₂4-OCF₃ 3-Cl Et H CH₂ 4-OCF₃ 3-Cl n-Pr H CH₂ 4-OCF₃ 3-Cl i-Pr H CH₂4-OCF₃ 3-Cl n-Bu H CH₂ 4-OCF₃ 3-Cl i-Bu H CH₂ 4-OCF₃ 3-Cl c-Pr H CH₂4-OCF₃ 3-Cl Ph H CH₂ 4-OCF₃ 3-Cl 4-Cl—Ph H CH₂ 4-OCF₃ 3-Cl 4-F—Ph H CH₂4-OCF₃ 3-Cl 4-CN—Ph H CH₂ 4-OCF₃ 3-Cl CO₂Me H CH₂ 4-OCF₃ 4-Br Me H CH₂4-OCF₃ 4-Br Et H CH₂ 4-OCF₃ 4-Br n-Pr H CH₂ 4-OCF₃ 4-Br i-Pr H CH₂4-OCF₃ 4-Br n-Bu H CH₂ 4-OCF₃ 4-Br i-Bu H CH₂ 4-OCF₃ 4-Br c-Pr H CH₂4-OCF₃ 4-Br Ph H CH₂ 4-OCF₃ 4-Br 4-Cl—Ph H CH₂ 4-OCF₃ 4-Br 4-F—Ph H CH₂4-OCF₃ 4-Br 4-CN—Ph H CH₂ 4-OCF₃ 4-Br CO₂Me H O 4-OCF₃ 4-Cl Me H O4-OCF₃ 4-Cl Et H O 4-OCF₃ 4-Cl n-Pr H O 4-OCF₃ 4-Cl i-Pr H O 4-OCF₃ 4-Cln-Bu H O 4-OCF₃ 4-Cl i-Bu H O 4-OCF₃ 4-Cl c-Pr H O 4-OCF₃ 4-Cl Ph H O4-OCF₃ 4-Cl 4-Cl—Ph H O 4-OCF₃ 4-Cl 4-F—Ph H O 4-OCF₃ 4-Cl 4-CN—Ph H O4-OCF₃ 4-Cl CO₂Me H O 4-CF₃ 4-Cl Me H O 4-CF₃ 4-Cl Et H O 4-CF₃ 4-Cln-Pr H O 4-CF₃ 4-Cl i-Pr H O 4-CF₃ 4-Cl n-Bu H O 4-CF₃ 4-Cl i-Bu H O4-CF₃ 4-Cl c-Pr H O 4-CF₃ 4-Cl Ph H O 4-CF₃ 4-Cl 4-Cl—Ph H O 4-CF₃ 4-Cl4-F—Ph H O 4-CF₃ 4-Cl 4-CN—Ph H O 4-CF₃ 4-Cl CO₂Me H O 4-OCF₃ 4-CF₃ Me HO 4-OCF₃ 4-CF₃ Et H O 4-OCF₃ 4-CF₃ n-Pr H O 4-OCF₃ 4-CF₃ i-Pr H O 4-OCF₃4-CF₃ n-Bu H O 4-OCF₃ 4-CF₃ i-Bu H O 4-OCF₃ 4-CF₃ c-Pr H O 4-OCF₃ 4-CF₃Ph H O 4-OCF₃ 4-CF₃ 4-Cl—Ph H O 4-OCF₃ 4-CF₃ 4-F—Ph H O 4-OCF₃ 4-CF₃4-CN—Ph H O 4-OCF₃ 4-CF₃ CO₂Me H O 4-CF₃ 4-CF₃ Me H O 4-CF₃ 4-CF₃ Et H O4-CF₃ 4-CF₃ n-Pr H O 4-CF₃ 4-CF₃ i-Pr H O 4-CF₃ 4-CF₃ n-Bu H O 4-CF₃4-CF₃ i-Bu H O 4-CF₃ 4-CF₃ c-Pr H O 4-CF₃ 4-CF₃ Ph H O 4-CF₃ 4-CF₃4-Cl—Ph H O 4-CF₃ 4-CF₃ 4-F—Ph H O 4-CF₃ 4-CF₃ 4-CN—Ph H O 4-CF₃ 4-CF₃CO₂Me H CH₂ 4-OCF₃ 4-CF₃ Me H CH₂ 4-OCF₃ 4-CF₃ Et H H, H 4-OCF₃ 5-CF₃n-Pr H H, H 4-OCF₃ 5-CF₃ i-Pr H H, H 4-OCF₃ 5-CF₃ n-Bu H H, H 4-OCF₃5-CF₃ i-Bu H H, H 4-OCF₃ 5-CF₃ c-Pr H H, H 4-OCF₃ 5-CF₃ Ph H H, H 4-OCF₃5-CF₃ 4-Cl—Ph H H, H 4-OCF₃ 5-CF₃ 4-F—Ph H H, H 4-OCF₃ 5-CF₃ 4-CN—Ph HH, H 4-OCF₃ 5-CF₃ CO₂Me H H, H 4-CF₃ 5-CF₃ Me H H, H 4-CF₃ 5-CF₃ Et H H,H 4-CF₃ 5-CF₃ n-Pr H H, H 4-CF₃ 5-CF₃ i-Pr H H, H 4-CF₃ 5-CF₃ n-Ru H H,H 4-CF₃ 5-CF₃ i-Bu H H, H 4-CF₃ 5-CF₃ c-Pr H H, H 4-CF₃ 5-CF₃ Ph H H, H4-CF₃ 5-CF₃ 4-Cl—Ph H H, H 4-CF₃ 5-CF₃ 4-F—Ph H H, H 4-CF₃ 5-CF₃ 4-CN—PhH H, H 4-CF₃ 5-CF₃ CO₂Me H CH₂ 4-OCF₃ 4-CF₃ n-Pr Me CH₂ 4-OCF₃ 4-CF₃n-Pr Et CH₂ 4-OCF₃ 4-CF₃ n-Pr n-Pr CH₂ 4-OCF₃ 4-CF₃ n-Pr i-Pr CH₂ 4-OCF₃4-CF₃ n-Pr n-Bu CH₂ 4-OCF₃ 4-CF₃ n-Pr s-Bu CH₂ 4-OCF₃ 4-CF₃ n-Pr i-BuCH₂ 4-OCF₃ 4-Cl n-Pr Me CH₂ 4-OCF₃ 4-Cl n-Pr Et CH₂ 4-OCF₃ 4-Cl n-Prn-Pr CH₂ 4-OCF₃ 4-Cl n-Pr i-Pr CH₂ 4-OCF₃ 4-Cl n-Pr n-Ru CH₂ 4-OCF₃ 4-Cln-Pr s-Bu CH₂ 4-OCF₃ 4-Cl n-Pr i-Bu CH₂ 4-Br 4-Cl Me H CH₂ 4-Br 4-Cl EtH CH₂ 4-Br 4-Cl n-Pr H CH₂ 4-Br 4-Cl i-Pr H CH₂ 4-Br 4-Cl n-Bu H CH₂4-Br 4-Cl i-Bu H CH₂ 4-Br 4-Cl c-Pr H CH₂ 4-Br 4-Cl Ph H CH₂ 4-Br 4-Cl4-Cl—Ph H CH₂ 4-Br 4-Cl 4-F—Ph H CH₂ 4-Br 4-Cl 4-CN—Ph H CH₂ 4-Br 4-ClCO₂Me H OCH₂ 4-OCF₃ 3-Cl n-Pr H CH₂O 4-OCF₃ 3-Cl n-Pr H S 4-OCF₃ 4-Cln-Pr H NH 4-OCF₃ 4-Cl n-Pr H CH₂CH₂ 4-OCF₃ 3-Cl n-Pr H NHCH₂ 4-OCF₃ 3-Cln-Pr H CH₂NH 4-OCF₃ 3-Cl n-Pr H

Formulation/Utility

Compounds of this invention will generally be used as a formulation orcomposition with an agriculturally suitable carrier comprising at leastone of a liquid diluent, a solid diluent or a surfactant. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature. Useful formulations include liquids such as solutions(including emulsifiable concentrates), suspensions, emulsions (includingmicroemulsions and/or suspoemulsions) and the like which optionally canbe thickened into gels. Useful formulations further include solids suchas dusts, powders, granules, pellets, tablets, films, and the like whichcan be water-dispersible (“wettable”) or water-soluble. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. Sprayableformulations can be extended in suitable media and used at spray volumesfrom about one to several hundred liters per hectare. High-strengthcompositions are primarily used as intermediates for furtherformulation.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water-  5-90  0-94  1-15 soluble Granules, Tablets and Powders.Suspensions, Emulsions, Solutions  5-50 40-95  0-15 (includingEmulsifiable Concentrates) Dusts  1-25 70-99 0-5 Granules and Pellets0.01-99      5-99.99  0-15 High Strength Compositions 90-99  0-10 0-2

Typical solid diluents are described in Watkins, et al., Handbook ofInseticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell,N.J. Typical liquid diluents are described in Marsden, Solvents Guide,2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents andEmulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J., as well asSisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ.Co., Inc., New York, 1964, list surfactants and recommended uses. Allformulations can contain minor amounts of additives to reduce foam,caking, corrosion, microbiological growth and the like, or thickeners toincrease viscosity.

Surfactants include, for example, polyethoxylated alcohols,polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acidesters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzenesulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates,naphthalene sulfonate formaldehyde condensates, polycarboxylates, andpolyoxyethylene/polyoxypropylene block copolymers. Solid diluentsinclude, for example, clays such as bentonite, montmorillonite,attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth,urea, calcium carbonate, sodium carbonate and bicarbonate, and sodiumsulfate. Liquid diluents include, for example, water,N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethyleneglycol, polypropylene glycol, paraffins, alkylbenzenes,alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn,peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4methyl-2-pentanone, and alcohols such as methanol,cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. Dusts and powders can be prepared byblending and, usually, grinding as in a hammer mill or fluid-energymill. Suspensions are usually prepared by wet-milling; see, for example,U.S. Pat. No. 3,060,084. Granules and pellets can be prepared byspraying the active material upon preformed granular carriers or byagglomeration techniques. See Browning, “Agglomeration”, ChemicalEngineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer'sHandbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 andfollowing, and WO 91/13546. Pellets can be prepared as described in U.S.Pat. No. 4,172,714. Water-dispersible and water-soluble granules can beprepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No.5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Filmscan be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see U.S. Pat.No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166,167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col.5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, JohnWiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., WeedControl Handbook, 8th Ed., Blackwell Scientific Publications, Oxford,1989.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Table A.

Example A Wettable Powder Compound 1 65.0% dodecylphenol polyethyleneglycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate6.0% montmorillonite (calcined) 23.0%. Example B Granule Compound 110.0% attapulgite granules (low volatile matter, 90.0%. 0.71/0.30 mm;U.S.S. No. 25-50 sieves) Example C Extruded Pellet Compound 1 25.0%anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodiumalkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.Example D Emulsifiable Concentrate Compound 1 20.0% blend of oil solublesulfonates 10.0% and polyoxyethylene ethers isophorone 70.0%.

The compounds of this invention exhibit activity against a wide spectrumof foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding,aquatic and soil-inhabiting arthropods (term “arthropods” includesinsects, mites and nematodes) which are pests of growing and storedagronomic crops, forestry, greenhouse crops, ornamentals, nursery crops,stored food and fiber products, livestock, household, and public andanimal health. Those skilled in the art will appreciate that not allcompounds are equally effective against all growth stages of all pests.Nevertheless, all of the compounds of this invention display activityagainst pests that include: eggs, larvae and adults of the OrderLepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding,seed-feeding larvae and adults of the Order Coleoptera; eggs, immaturesand adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphsand adults of the Order Acari; eggs, immatures and adults of the OrdersThysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults ofthe Order Diptera; and eggs, juveniles and adults of the PhylumNematoda. The compounds of this invention are also active against pestsof the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanuraand Psocoptera; pests belonging to the Class Arachnida and PhylumPlatyhelminthes. Specifically, the compounds are active against southerncorn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper(Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spottedspider mite (Tetranychus urticae), fall armyworm (Spodopterafrugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzuspersica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphisnoxia), English grain aphid (Sitobion avenae), tobacco budworm(Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus),rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper(Nilaparvata lugens), small brown planthopper (Laodelphax striatellus),rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocismedinalis), black rice stink bug (Scotinophara lurida), rice stink bug(Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug(Cletus puntiger), and southern green stink bug (Nezara viridula). Thecompounds are active on mites, demonstrating ovicidal, larvicidal andchemosterilant activity against such families as Tetranychidae includingTetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli,Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus,Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis,Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychusyumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidaeincluding Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpuscalifornicus and Brevipalpus obovatus; Eriophyidae includingPhyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus,Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO92/00673 for more detailed pest descriptions.

Compounds of this invention can also be mixed with one or more otherinsecticides, fungicides, nematocides, bactericides, acaricides, growthregulators, chemosterilants, semiochemicals, repellents, attractants,pheromones, feeding stimulants or other biologically active compounds toform a multi-component pesticide giving an even broader spectrum ofagricultural protection. Examples of such agricultural protectants withwhich compounds of this invention can be formulated are: insecticidessuch as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin,carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin,diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate,fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate,tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion,metaldehyde, methamidophos, methidathion, methomyl, methoprene,methoxychlor, methyl7-Chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylate(DPX-JW062), monocrotophos, oxamyl, parathion, parathion-methyl,permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb,profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos,tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon andtriflumuron; fungicides such as acibenzolar, azoxystrobin, binomial,blasticidin-S, Bordeaux mixture (Triassic copper sulfate),bromuconazole, capropamid (KTU 3616), captafol, captan, carbendazim,chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil,cyproconazole, cyprodinil (CGA 219417),(S)-3,5-dichloro-N-(3-Chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH 7281), diclocymet (S-2900), diclomezine, dicloran,difenoconazole,(S)-3,5-dihydro-5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one(RP 407213), dimethomorph, diniconazole, diniconazole-M, dodine,edifenphos, epoxiconazole (BAS 480F), famoxadone, fenarimol,fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil,flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil,flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658),hexaconazole, ipconazole, iprobenfos, iprodione, isoprothidlane,kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil,metalaxyl, metconazole, metominostrobin/fenominostrobin (SSF-126),myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl,penconazole, pencycuron, probenazole, prochloraz, propamocarb,propiconazole, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen,spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, triadimefon, triadimenol,tricyclazole, triticonazole, validamycin and vinclozolin; nematocidessuch as aldoxycarb and fenamiphos; bactericides such as streptomycin;acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin,dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide,fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben andtebufenpyrad; and biological agents such as Bacillus thuringiensis,Bacillus thuringiensis delta endotoxin, baculovirus, andentomopathogenic bacteria, virus and fungi.

In certain instances, combinations with other arthropodicides having asimilar spectrum of control but a different mode of action will beparticularly advantageous for resistance management.

Arthropod pests are controlled and protection of agronomic,horticultural and specialty crops, animal and human health is achievedby applying one or more of the compounds of this invention, in aneffective amount, to the environment of the pests including theagronomic and/or nonagronomic locus of infestation, to the area to beprotected, or directly on the pests to be controlled. Thus, the presentinvention further comprises a method for the control of foliar and soilinhabiting arthropods and nematode pests and protection of agronomicand/or nonagronomic crops, comprising applying one or more of thecompounds of the invention, or compositions containing at least one suchcompound, in an effective amount, to the environment of the pestsincluding the agronomic and/or nonagronomic locus of infestation, to thearea to be protected, or directly on the pests to be controlled. Apreferred method of application is by spraying. Alternatively, granularformulations of these compounds can be applied to the plant foliage orthe soil. Other methods of application include direct and residualsprays, aerial sprays, seed coats, microencapsulations, systemic uptake,baits, eartags, boluses, foggers, fumigants, aerosols, dusts and manyothers. The compounds can be incorporated into baits that are consumedby the arthropods or in devices such as traps and the like.

The compounds of this invention can be applied in their pure state, butmost often application will be of a formulation comprising one or morecompounds with suitable carriers, diluents, and surfactants and possiblyin combination with a food depending on the contemplated end use. Apreferred method of application involves spraying a water dispersion orrefined oil solution of the compounds. Combinations with spray oils,spray oil concentrations, spreader stickers, adjuvants, other solvents,and synergists such as piperonyi butoxide often enhance compoundefficacy.

The rate of application required for effective control will depend onsuch factors as the species of arthropod to be controlled, the pest'slife cycle, life stage, its size, location, time of year, host crop oranimal, feeding behavior, mating behavior, ambient moisture,temperature, and the like. Under normal circumstances, application ratesof about 0.01 to 2 kg of active ingredient per hectare are sufficient tocontrol pests in agronomic ecosystems, but as little as 0.001 kg/hectaremay be sufficient or as much as 8 kg hectare may be required. Fornonagronomic applications, effective use rates will range from about 1.0to 50 mg/square meter but as little as 0.1 mg/square meter may besufficient or as much as 150 mg/square meter may be required.

The following TESTS demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of arthropod development (including mortality) that causessignificantly reduced feeding. The pest control protection afforded bythe compounds is not limited, however, to these species. See Index TableA for compound descriptions. The following abbreviations are used in theIndex Table that follows: n is normal, i is iso, Pr ispropyl, and Ph isphenyl. The abbreviation “Ex.” stands for “Example” and is followed by anumber indicating in which example the compound is prepared.

INDEX TABLE A

Cmpd No. (R¹)_(m) (R²)_(n) R³ R⁷ mp ° C.  1 4-OCF₃ 4-Cl n-Pr H 167-170 2 4-Br 4-Cl n-Pr H 185-186 3 (Ex. 1) 4-OCF₃ 4-CF₃ n-Pr H 192-194 4 (Ex.2) 4-Br 4-CF₃ n-Pr H 198-199  5 4-CF₃ 4-Cl n-Pr CH₃ 91-93  6 4-OCF₃ 4-Cln-Pr CH₃ 67-72  7 4-CF₃ 4-CF₃ n-Pr CH₃ 124-126  8 4-OCF₃ 4-CF₃ n-Pr CH₃75-77  9 4-CF₃ 4-CF₃ CH₃ CH₃ 80-82 10 4-OCF₃ 4-CF₃ CH₃ CH₃ 80-90 114-CF₃ 4-CF₃ n-Pr COCH₃ 182-184 12 4-OCF₃ 4-CF₃ n-Pr COCH₃ 128-130 134-OCF₃ 4-F 4-FPh H 189-191 14 4-OCF₃ 4-F CH₃ H 211-212 15 4-OCF₃ 4-Cli-Pr H 178-179 16 4-OCF₃ 4-F 4-FPh CO₂CH₃ 104-106 17 4-OCF₃ 4-F CH₃ CH₃169-171 18 4-OCF₃ 4-F CH₃ CO₂CH₃ 83-85 19 4-CF₃ 4-F CH₃ CH₃ 133-134 204-SCF₃ 4-Cl n-Pr H 190-191 21 4-SCF₃ 4-CF₃ n-Pr H 200-202 22 4-SCF₃ 4-F4-FPh H 195-196 23 4-SCF₃ 4-F CH₃ H 136-138 24 3,4-OCF₂O— 4-Cl n-Pr H180-181 25 3,4-OCF₂O— 4-CF₃ n-Pr H 125-128 26 3,4-OCF₂O— 4-F CH₃ H110-113 27 3,4-OCF₂O— 4-Cl i-Pr H 201-202

BIOLOGICAL EXAMPLES OF THE INVENTION TEST A

Fall Armyworm

Test units, each consisting of a H.I.S. (high impact styrene) tray with16 cells were prepared. Wet filter paper and approximately 8 cm² of limabean leaf were placed into twelve of the cells. A 0.5-Cm layer of wheatgerm diet was placed into the four remaining cells. Fifteen to twentythird-instar larvae of fall armyworm (Spodoptera frugiperda) were placedinto a 230-mL (8-ounce) plastic cup. Solutions of each of the testcompounds in 75:25 acetone-distilled water solvent were sprayed into thetray and cup. Spraying was accomplished by passing the tray and cup on aconveyer belt directly beneath a flat fan hydraulic nozzle whichdischarged the spray at a rate of 0.138 kilograms of active ingredientper hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). Theinsects were transferred from the 230-mL cup to the H.I.S. tray (oneinsect per cell). The trays were covered and held at 27° C. and 50%relative humidity for 48 hours, after which time readings were taken onthe twelve cells with lima bean leaves. The four remaining cells wereread at 6-8 days for delayed toxicity. Of the compounds tested, thefollowing gave control efficacy levels of 80% or greater: 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 22, 24, 25 and27.

TEST B

Tobacco Budworm

The test procedure of TEST A was repeated for determining efficacyagainst third-instar larvae of the tobacco budworm (Heliothis virescens)except that three 230-mL (8-ounce) plastic cups with wheat germ dietwere used in place of the H.I.S. tray, with each cup pre-infected withfive third-instar larvae. Of the compounds tested, the following gavemortality levels of 80% or higher: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 19, 20, 21, 22, 24, 25 and 27.

What is claimed is:
 1. A compound selected from Formula I, N-oxides andagriculturally suitable salts thereof,

wherein: A is H; E is H or C₁-C₃ alkyl; or A and E can be taken togetherto form —CH₂—, —CH₂CH₂—, —O—, —S—, —S(O)—, —S(O)₂—, —NR⁸, —OCH₂—,—SCH₂—, —N(R⁸)CH₂—, substituted —CH₂— and substituted —CH₂CH₂—, thesubstituents independently selected from 1-2 halogen and 1-2 methyl; Gis selected from the group consisting of

W is N; X is NR⁷; Y is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₁-C₃ alkylsulfonyl, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, NR⁹R¹⁰,N═CR¹¹R¹², OR⁷, COR¹³, CO₂R¹⁴ or C₁-C₆ alkyl substituted by at least onegroup selected from halogen, C₁-C₃ alkoxy, CN, NO₂, S(O)_(r)R¹⁵, COR¹³,CO₂R¹⁴ and optionally substituted phenyl; Z is O or S; each R¹ and R² isindependently selected from the group consisting of C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, halogen, CN, NO₂, OR¹⁶, S(O)_(r)R¹⁵, OS(O)₂R¹⁵,CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, SO₂NR⁹R¹⁰, SF₅, optionally substitutedphenyl and optionally substituted benzyl; or when m or n is 2, (R¹)₂ canbe taken together or (R²)₂ can be taken together as —OCH₂O—, —OCF₂O—,—OCH₂CH₂O—, —CH₂C(CH₃)₂O—, —CF₂CF₂O or —OCF₂CF₂O—; R³ is selected fromthe group consisting of J, C(R¹⁷)═N—O—R¹⁸, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxylalkyl,C₃-C₈ alkoxycarbonylalkyl, CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, C(S)NR⁹R¹⁰,C(S)R¹³, C(S)SR¹³, CN, and optionally substituted phenyl; or R³ is C₂-C₆epoxyalkyl optionally substituted with a group selected from C₁-C₃alkyl, CN, C(O)R¹³, CO₂R¹⁴ and optionally substituted phenyl; or R³ isC₁-C₆ alkyl substituted with a group selected from C(O)NR⁹R¹⁰, COR¹³,CO₂R¹⁴, S(O)_(m)R¹⁵, SCN, CN, C₁-C₂ haloalkoxy, SiR¹⁹R²⁰R²¹, NR⁹R¹⁰,NO₂, OC(O)R¹³, —P(O)(OR²²)₂, optionally substituted phenyl, and J; J isa nonaromatic or aromatic 5- or 6-membered heterocyclic ring, bondedthrough carbon or nitrogen, containing 1-4 heteroatoms independentlyselected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4nitrogen, optionally containing one carbonyl moiety and optionallysubstituted; each R⁷ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy, SO₂NR⁹R¹⁰, SO₂R¹³, COR⁹,CONR⁹R¹⁰, CO₂R¹³, optionally substituted phenyl or optionallysubstituted benzyl; each R⁸ is independently H, C₁-C₄ alkyl, C₁-C₄alkoxyalkyl, CO₂R¹³, SO₂R¹³, or optionally substituted benzyl; each R⁹and each R¹¹ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl oroptionally substituted phenyl; each R¹⁰ and each R¹² is independently Hor C₁-C₄ alkyl; or each pair of R⁹ and R¹⁰ when attached to the sameatom or each pair of R¹¹ and R¹² when attached to the same atomindependently can be taken together as —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—,—CH₂CH₂CH₂CH₂CH₂— or —CH₂CH₂OCH₂CH₂—, each of which is optionally andindependently substituted with 1 or 2 CH₃ groups; each R¹³ and each R¹⁵is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or optionallysubstituted phenyl; each R¹⁴ is independently H, C₁-C₄ alkyl, C₁-C₄haloalkyl or optionally substituted benzyl; R¹⁶ is H, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₃-C₆haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl, C₁-C₆ nitroalkyl,C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, optionally substituted phenyl and optionally substitutedbenzyl; R¹⁷ is selected from the group consisting of H, Cl, C₁-C₄ alkyl,C₁-C₄ alkoxy, C₁-C₂ thioalkyl and CN; R¹⁸ is selected from the groupconsisting of H, C₁-C₄ alkyl, C₂-C₃ alkylcarbonyl and C₂-C₃alkoxycarbonyl; R¹⁹ and R²⁰ are each independently C₁-C₃ alkyl; R²¹ isselected from the group consisting of H, C₁-C₃ alkyl and optionallysubstituted phenyl; each R²² is independently H or C₁-C₄ alkyl; each mand n are independently 1 to 3; and r is 0, 1 or
 2. 2. A compound ofclaim 1 wherein Y is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₃alkylsulfonyl, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkylalkyl, NR⁹R¹⁰,N═CR¹¹R¹², OR⁷, COR¹³, CO₂R¹⁴ or C₁-C₆ alkyl substituted by at least onegroup selected from halogen, C₁-C₃ alkoxy, CN, NO₂, S(O)_(r)R¹⁵, COR¹³,CO₂R¹⁴ and phenyl optionally substituted with R²³ and R²⁴; each R¹ andR² is independently selected from the group consisting of C₁-C₆haloalkyl, C₂-C₆ haloalkenyl, halogen, CN, NO₂, OR¹⁶, S(O)_(r)R¹⁵,OS(O)₂R¹⁵, CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, SO₂NR⁹R¹⁰, SF₅, phenyloptionally substituted with R²³ and R²⁴ and benzyl optionallysubstituted with R²³ and R²⁴; or when m or n is 2, (R¹)₂ can be takentogether or (R²)₂ can be taken together as —OCH₂O—, —OCF₂O—, —OCH₂CH₂O—,—CH₂C(CH₃)₂—, —CF₂CF₂O or —OCF₂CF₂O—; R³ is selected from the groupconsisting of J, C(R¹⁷)═N—O—R¹⁸, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆alkenyl, C₂-C₆ haloalkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxylalkyl, C₃-C₈alkoxycarbonylalkyl, CO₂R¹⁴, C(O)R¹³, C(O)NR⁹R¹⁰, C(S)NR⁹R¹⁰, C(S)R¹³,C(S)SR¹³, CN, and phenyl optionally substituted with R²³ and R²⁴; or R³is C₂-C₆ epoxyalkyl optionally substituted with a group selected fromC₁-C₃ alkyl, CN, C(O)R¹³, and CO₂R¹⁴ and phenyl optionally substitutedwith R²³ and R²⁴; or R³ is C₁-C₆ alkyl substituted with a group selectedfrom C(O)NR⁹R¹⁰, COR¹³, CO₂R¹⁴, S(O)_(m)R¹⁵, SCN, CN, C₁-C₂ haloalkoxy,SiR¹⁹R²⁰R²¹, NR⁹R¹⁰, NO₂, OC(O)R¹³, —P(O)(OR²²)₂, phenyl optionallysubstituted with R²³ and R²⁴, and J; J is a nonaromatic or aromatic 5-or 6-membered heterocyclic ring, bonded through carbon or nitrogen,containing 1-4 heteroatoms independently selected from the groupconsisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, optionallycontaining one carbonyl moiety and optionally substituted with R²³ andR²⁴; each R⁷ is independently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy, SO₂NR⁹R¹⁰, SO₂R¹³, COR⁹, CONR⁹R¹⁰,CO₂R¹³, phenyl optionally substituted with R²³ and R²⁴ or benzyloptionally substituted with R²³ and R²⁴; each R⁸ is independently H,C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl, CO₂R¹³, SO₂R¹³, or benzyl optionallysubstituted with R²³ and R²⁴; each R⁹ and each R¹¹ is independently H,C₁-C₄ alkyl, C₁-C₄ haloalkyl or phenyl optionally substituted with R²³and R²⁴; each R¹⁰ and each R¹² is independently H or C₁-C₄ alkyl; oreach pair of R⁹ and R¹⁰ when attached to the same atom or each pair ofR¹¹ and R¹² when attached to the same atom independently can be takentogether as —CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH₂CH₂CH₂— or—CH₂CH₂OCH₂CH₂—, each of which is optionally and independentlysubstituted with 1 or 2 CH₃ groups; each R¹³ and each R¹⁵ isindependently H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or phenyl optionallysubstituted with R²³ and R²⁴; each R¹⁴ is independently H, C₁-C₄ alkyl,C₁-C₄ haloalkyl or benzyl optionally substituted with R²³ and R²⁴; R¹⁶is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ haloalkenyl,C₂-C₆ alkynyl, C₃-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyloptionally substituted with R²³ and R²⁴ and benzyl optionallysubstituted with R²³ and R²⁴; R²¹ is selected from the group consistingof H, C₁-C₃ alkyl and phenyl optionally substituted with R²³ and R²⁴;each R²³ is independently selected from the group consisting of 1-2,halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyland C₁-C₂ haloalkylsulfonyl; and each R²⁴ is independently selected fromthe group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄haloalkyl and C₁-C₄ haloalkoxy.
 3. The compound of claim 2 which is7-Chloro-9,9α-dihydro-9α-propyl-N-[4-(trifluoromethoxy)phenyl]-1H-indeno[1,2-e]-1,2,4-triazine-3-carboxamide.4. An arthropodicidal composition comprising an arthropodicidallyeffective amount of a compound of claim 1 and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents.
 5. A method for controlling arthropodscomprising contacting the arthropods or their environment with anarthropodicidally effective amount of a compound of claim 1.